EP1054256B1 - Adapteur pour désorption des tubes d'échantillonnage, arrangement d'un chromatographe en phase gazeuse et d'un adaptateur, et arrangement de pièces pour former un tel assemblage - Google Patents

Adapteur pour désorption des tubes d'échantillonnage, arrangement d'un chromatographe en phase gazeuse et d'un adaptateur, et arrangement de pièces pour former un tel assemblage Download PDF

Info

Publication number
EP1054256B1
EP1054256B1 EP00201813A EP00201813A EP1054256B1 EP 1054256 B1 EP1054256 B1 EP 1054256B1 EP 00201813 A EP00201813 A EP 00201813A EP 00201813 A EP00201813 A EP 00201813A EP 1054256 B1 EP1054256 B1 EP 1054256B1
Authority
EP
European Patent Office
Prior art keywords
sampling tube
adapter
injector
carrier gas
tube
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP00201813A
Other languages
German (de)
English (en)
Other versions
EP1054256A1 (fr
Inventor
Marinus Frans Van Der Maas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SGT Exploitatie BV
Original Assignee
SGT Exploitatie BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SGT Exploitatie BV filed Critical SGT Exploitatie BV
Publication of EP1054256A1 publication Critical patent/EP1054256A1/fr
Application granted granted Critical
Publication of EP1054256B1 publication Critical patent/EP1054256B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N30/12—Preparation by evaporation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N30/12—Preparation by evaporation
    • G01N2030/126—Preparation by evaporation evaporating sample
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/24—Automatic injection systems

Definitions

  • sampling tubes It is well known to store samples of gases, liquids or like fluids in so-called sampling tubes. To that end, see, for instance, EP-A-0 816 823 . Also solid substance in the form of granules or the like is stored in sampling tubes. Often, but not always, such sampling tubes are filled with absorption material in which the gas or the liquid, at least the substances present therein, are absorbed. Such sampling tubes are used, for instance, in surroundings where the danger exists that the atmosphere becomes contaminated, as in, for instance, laboratories, chemical factories, submarines and the like. Thus there are sampling tubes where the air to be measured is actively pumped through the sampling tube and where the sampling tube is therefore provided with an inflow opening and an outflow opening.
  • the gas When a sample of a gas to be sampled is being taken, the gas is pumped into the inflow opening, and the gas leaves the sampling tube via the outflow opening while leaving the substances contained in the gas behind in the absorption material.
  • This procedure of sampling is designated as active sampling. Also known, from practice, is so-called passive sampling. In that case the sampling tubes have only one inflow opening during sampling. The air or the gas to be sampled diffuses via that opening into the absorption material while leaving the substances contained in the gas behind in the absorption material.
  • the sampling tube After some time has passed after sampling, the sampling tube is desorbed. To that end, heretofore, use has been made of special devices which are particularly costly. Desorption of the sampling tube occurs by heating the sampling tube, so that the substances present in the absorption material or in the solid substance contained in the sampling tube evaporate and are liberated. By blowing a carrier gas through the sampling tube during heating, the liberated substances are entrained by the carrier gas and can, for instance, be temporarily collected in a cold trap and subsequently be passed from the cold trap to a gas chromatograph in which the gases released can be analyzed.
  • the known desorption devices are therefore provided with carrier gas supply means, heating means, a cold trap, control means for controlling the heating means and the like. This has as a result that the known desorption devices have a considerable cost price, which are of the order of a few tens of thousands of guilders.
  • the invention envisages an entirely new type of assembly by means of which sampling tubes can be desorbed, and which has a much lower cost price.
  • the invention is based on the insight that the gas chromatograph, which is necessary anyhow, essentially has all the means that are also used in a known desorption device. By means of the assembly, these means already present in the gas chromatograph are made available for desorbing sampling tubes.
  • the invention provides an adaptor according to claim 1 and an assembly according to claim 5.
  • the temperature of the sampling tube contained in the chamber of the adapter can be accurately controlled, so that any particular temperature course of the sampling tube can be realized very accurately.
  • first the light fractions contained in the sampling tube can be released by heating the sampling tube to, for instance, 50°C for some time, whereafter subsequently heavier fractions can be liberated by heating the sampling tube to, for instance, 150°-250°C.
  • the adapter is provided with a heat conducting tube which is connected with the heat conducting housing, such that the tube and the housing are in heat exchange with each other, while the tube of the adapter, in the fitted condition of the adapter, reaches into the injector chamber. Because the tube reaches into the injector chamber, the heat transfer from the heating means of the injector will occur much more efficiently in that the tube of the adapter is directly surrounded by the heating means of the injector.
  • the assembly further comprises an autosampler known per se, which autosampler comprises a setup rack in which a number of vial-shaped sampling tubes can be set up, while the manipulator of the autosampler is arranged for picking up a sampling tube from the setup rack and placing such sampling tube in the adapter.
  • the autosampler known per se is used to spout a liquid sample contained in a vial from this vial into the injector.
  • the manipulator of the autosampler moves the vial in question from the setup rack into what is designated in practice by the term turret, from where an automatically operable spout sucks up the sample from the vial and then injects it into the injector of the gas chromatograph.
  • the autosampler in most cases already present can be used for converting the gas chromatograph to a sampling tube desorbing device.
  • the invention relates to a kit of parts comprising at least one adapter according to the invention, as well as a support for mounting an autosampler known per se on a gas chromatograph known per se.
  • the support may be designed such that the autosampler can place the sampling tubes in the adapter, which is placed in an injector of the gas chromatograph, without requiring adjustment of the control of the autosampler.
  • the kit also comprises various carrier gas ducts, at least one T-piece and a valve assembly.
  • the gas chromatograph represented in Fig. 1 is marketed by Hewlett Packard® and comprises a housing 2 in which an oven chamber is included which is closed off with an oven door 3.
  • the housing 2 further contains a control which is operable by means of the control panel 4.
  • two, gas chromatography columns may be disposed, which are generally designed as capillary tubes provided with an internal coating.
  • Such gas chromatography columns 42 are connected by an inlet end to a so-called injector 5 and by an outlet end to a so-called detector 6.
  • two detectors 6 are represented and two openings 7 in the top of the housing 2 for the purpose of injectors 5.
  • the injectors 5 are provided with heating means in the form of a spiral filament which extends around an injector chamber into which normally the liquid to be analyzed is injected.
  • a so-called autosampler which is mounted on the upper left corner of the gas chromatograph 1.
  • Such an autosampler 8 is represented in perspective in Fig. 2 and comprises inter alia a setup rack 9 provided with a large number of openings 10 for receiving vials 11.
  • a vial 11 is a vessel in which a liquid sample can be stored.
  • an exemplary embodiment of a vial 11 is represented in Fig. 3 , with the specified dimensions being indicated in millimeters.
  • the autosampler 8 further comprises an arm 12 which carries a gripper 13.
  • the gripper 13 is provided with a gripper jaw 14 by means of which, in the use according to the prior art, vial 11 can be picked up from the tray 9.
  • the vial 11 can then be moved past a reader 15, so that a code carried by the vial can be read.
  • This turret 16 is situated under a tower 17.
  • this tower 17 Disposed in this tower 17 is an automatically energized injection needle by means of which liquid can be sucked up from a vial 11 which is disposed in the turret 16 and subsequently can be injected into the injector 5 of the gas chromatograph 1.
  • the turret 16 mostly contains other liquid reservoirs with cleaning liquid for cleaning the injection needle after it has sucked up a sample from a vial 11 and delivered it to the injector 5. All devices discussed so far with reference to the drawings belong to the state of the art and are marketed inter alia by Hewlett Packard®.
  • Fig. 5 shows the housing 18, bounding the injector chamber, of the injector known per se.
  • an adapter 19 is placed in which a sampling tube 20 is received.
  • the adapter 19 is connected with the housing 18 of the injector chamber by means of a retaining nut 21, which housing 18 forms part of a standard injector.
  • the housing 18 is provided with a so-called split-off channel 22 which is in fluid communication with the interior of the injector chamber.
  • a needle 23 is clearly shown, in which a capillary duct 24 extends as far as an outflow opening 25 of the sampling tube 20.
  • An inflow opening 26 of the sampling tube 20 is in fluid communication with the injector chamber which is bounded by the housing 18.
  • a sealing ring 27 is provided, which is clamped between the adapter 19 and the injector chamber housing 18.
  • Fig. 6 shows the adapter 19, the fastening nut 21 and the sealing ring 27 in disassembled condition.
  • the adapter 19 of the present exemplary embodiment comprises a chamber K which is bounded by a heat conducting housing 29. Further, the adapter 19 comprises a heat conducting tube 30 which is connected with the housing 29 such that they are in heat exchange with each other. In the present exemplary embodiment, the tube 30 and the housing 29 are constructed as a single integral part. Further, in the present exemplary embodiment, in the wall of the tube 30 a bore 28 is provided which, in the condition of the adapter 19 when fitted in the injector 18, is in fluid communication with the split-off channel 22 of the injector housing 18, as is clearly represented in Fig. 5 .
  • the adapter is not provided with a heat conducting tube which reaches into the injection chamber bounded by the injector housing 18. To bring the temperature in the chamber K of the adapter to the desired value, it is then necessary that the heating means of the injector 5 are set at a higher temperature. It is self-explanatory that a design with heat conducting tube 30 is preferred.
  • the housing 29 of the adapter comprises a collar 31 which is engaged by the fastening nut 21 and against which the sealing ring 27 abuts when the adapter is mounted on the injector housing 18.
  • Fig. 7 shows an exemplary embodiment of a sampling tube 20 which can be used in the adapter 19 which is represented in Figs. 5 and 6 .
  • the sampling tube 20 represented in Fig. 7 has substantially the same dimensions as the vial 1 which is represented in Fig. 3 . Consequently, the sampling tubes 20 can be accommodated in the openings 10 of the setup rack 9 and be effectively engaged by the gripper 13 of the manipulator 12, 13, 14 of the autosampler 8 known per se.
  • the sampling tube 20 which is represented in Fig. 7 is provided with an inflow opening 26 and an outflow opening 25 which are provided at the same end 20a of the sampling tube 20.
  • the sampling space B of the sampling tube 20 will generally contain an absorption material, such as, for instance, Tenax® (trademark of the firm Akzo; polyphenylene oxides).
  • an absorption material such as, for instance, Tenax® (trademark of the firm Akzo; polyphenylene oxides).
  • other absorption materials can also be selected, for instance activated carbon such as, for instance, carbographTM, carbosieveTM and carbotrapTM and other absorbing powders or granular materials such as silica gel, deactivated aluminum and the like.
  • the chamber B of the sampling tube 20 is filled with a solid substance in granular form on which the measurement itself is to be performed, such as for instance a ground plastic or the like.
  • a duct 32 Connected to the inflow opening 26 of the sampling tube 20 is a duct 32 having a first end 32a.
  • the duct 32 extends through the inner chamber B of the sampling tube 20 and terminates through a second end 32b adjacent a second end 20b of the sampling tube, located opposite the first end 20a of the sampling tube.
  • the first end 20a of the sampling tube 20 is provided with a first sealing ring 33 which is adapted for creating a fluid-tight seal between the tapering underside K1 of the chamber K of the adapter 19.
  • the end 20a of the sampling tube 20 is provided with a second sealing ring 34 which connects in a fluid-tight manner to a capillary 35 which is inserted into the outflow opening 25 of the sampling tube 20.
  • FIG. 8 shows clearly the manner in which the sealing rings 33 and 34 cooperate respectively with the tapered underside K1 of the chamber K and a capillary column 35 reaching into the inflow opening. Further, it is clear from Fig. 8 in what way the fastening nut 21 secures the adapter 19 to the injector housing 18, with the sealing ring 27 forming a seal. Also visible is the bore 28 in the wall of the tube 30 of the adapter 19 and the manner in which it has been set in fluid communication with the split-off channel 22 of the injector.
  • a needle 36 reaches at least into the underside K1 of the chamber K of the adapter. This hollow needle 36 surrounds the capillary 35 which reaches slightly further into the chamber K of the adapter.
  • the capillary 35 When placing a sampling tube 20 in the adapter 19, the capillary 35 is automatically pushed beyond the sealing ring 34, so that a fluid communication between the capillary 35 and the inner chamber B of the sampling tube is effected.
  • the inflow opening 26 of the sampling tube 20 is in fluid communication with the inner space S of the tube 30, which is fluid-tightly closed at the lower end, where it allows only the needle 36 and the capillary 35 to pass. In that way, therefore, a fluid communication is created between the inflow opening 26 and the split-off channel 22 of the injector 5.
  • the carrier gas flows to the inflow opening 26 of the sampling tube 20 and via the duct 32 to a second end 20b of the sampling tube.
  • the carrier gas flows into the inner chamber B of the sampling tube and there will have to penetrate through the absorption material to reach the outflow opening 25.
  • the heating means of the injector chamber 5 are meanwhile heated up, so that the heat conducting tube 30 of the adapter 19 is heated.
  • the heat in the heat conducting tube 30 is passed on to the heat conducting housing 29 bounding the chamber K of the adapter 19. Consequently, the sampling tube 20 will rise in temperature, so that the substances contained in the absorption material are liberated by evaporation and entrained with the carrier gas.
  • the needle 36 or the inner space S of the heat conducting tube 30 the absorption tube is provided with a screen 37 adjacent the outflow opening.
  • the sampling tube 20 represented in Fig. 7 is suitable for active sampling.
  • a pump is connected to the first end 20a of the sampling tube 20, which pumps the gas to be sampled via the inflow opening 26 into the sampling tube 20 or sucks the gas to be sampled from the outflow opening 25 through the sampling tube 20.
  • the sampling tube 20 for passive desorption.
  • the first end 20a is closed off by means of a cap and the closing plate 38 is replaced with a screen.
  • the gas to be sampled can, by diffusion, diffuse into the interior B of the sampling tube 20.
  • the screen adjacent the second end 20b is replaced by a closing plate 38 and the cap which closes off the first end 20a of the sampling tube 20 is removed.
  • the sampling tube 20 is preferably made of inert material, such as, for instance, glass, metal, ceramics, Teflon® (PTFE) or Vespel® (both trademarks of Dupont).
  • inert material such as, for instance, glass, metal, ceramics, Teflon® (PTFE) or Vespel® (both trademarks of Dupont).
  • PTFE Teflon®
  • Vespel® both trademarks of Dupont
  • a transponder may be included in which an identification code and/or data about the sampling are stored. While the sampling tube is being placed from the setup rack 9 in the adapter 19, the transponder can be momentarily read in the reader 15 (see Fig. 2 ), so that the gas chromatograph 1 can run the correct program for desorbing the tube 20 in question.
  • Figs. 9 and 10 show a schematic view of the assembly.
  • Fig. 9 shows the desorption phase and Fig. 10 the analysis phase.
  • Figs. 9 and 10 schematically show the gas chromatograph 1 with the injector 5 on the left-hand side and the detector 6 on the right-hand side.
  • the injector 5 and the detector 6 are in fluid communication with each other, inter alia via the gas chromatography column 42.
  • an adapter 19 as described hereinbefore is placed.
  • a sampling tube 20 is placed in the chamber K of the adapter 19, a sampling tube 20 is placed.
  • the inlet 26 of the sampling tube 20 in fluid communication with a first carrier gas duct 41 which is connected to the split-off channel 22 of the injector 5.
  • the split-off channel 22 is also clearly represented in Fig.
  • the other end of the first carrier gas supply duct 41 is connected with a first outlet 43b of a valve assembly 43, which in the present exemplary embodiment is designed as a three-way valve.
  • the inlet 43a of the three-way valve 43 is connected with a carrier gas main supply duct 45.
  • a second outlet 43c of the three-way valve 43 is connected to a second carrier gas supply duct 44.
  • the three-way valve 43 sets the carrier gas main supply duct 45 in fluid communication with either the first carrier gas supply duct 41 or the second carrier gas supply duct 44. It is evident that the valve assembly 43 can also be designed as two single valves.
  • the assembly further comprises a cold trap 46 which is arranged in the oven chamber O of the gas chromatograph 1.
  • Such a cold trap 46 is formed by a capillary duct which is surrounded by a jacket which jacket is cooled by means of, for instance, liquid nitrogen. As a result of the very low temperature prevailing in the cold trap 46, all substances desorbed from the sampling tube 20 will condense therein and be retained. As soon as the cooling of the cold trap 46 is switched off, and the capillary is heated up by means of the oven of the gas chromatograph 1, the substances condensed in the cold trap 46 will evaporate again and be liberated for analysis.
  • the assembly further comprises a first connecting duct 47 which sets the capillary discharge 35 of the injector 5 in fluid communication with an inlet 46a of the cold trap 46.
  • a second connecting duct 48 connects an outlet 46b of the cold trap 46 with the gas chromatography column 42.
  • the discharge 35, the first connecting duct 47, the cold trap 46 and the second connecting duct 48 are preferably designed as a capillary duct in which upstream and downstream of the cold trap, respectively, a first T-junction 49 and a second T-junction 50 are provided.
  • Connected to the first T-junction 49 is an outlet of the second carrier gas supply duct 44, while a discharge duct 51 is connected to the second T-junction 50.
  • the T-junctions 49, 50 can be designed in a variety of ways and are known per se.
  • the three-way valve 43 is set in a position such that the carrier gas main supply duct 45 is in fluid communication with the first carrier gas supply duct 41.
  • the carrier gas flows via the split-off channel 22 of the injector 5 into the interior of the tube 30 of the adapter and from there via the inflow opening 26 of the sampling tube 20 and the duct 32 in the sampling tube 20 into the interior B of the sampling tube.
  • the carrier gas proceeds to flow through the absorption material in the sampling tube 20 to the outflow opening 25 which is connected to the capillary 35 which forms the outlet or discharge of the injector.
  • This capillary 35 leads to the first T-junction 49 and is in fluid communication with the first connecting duct 47 which leads to the cold trap 46.
  • the adapter 19 is heated by the heating means of the injector 7, substances contained in the absorption material will be liberated and be entrained with the carrier gas passed through the sampling tube 20.
  • This carrier gas flows to the cold trap 46 in which the substances condense from the carrier gas.
  • the three-way valve 3 can be set in the second position, which is shown in Fig. 10 . In this second position, the carrier gas main supply duct 45 is in fluid communication with the second carrier gas supply duct 44.
  • the heating means of the injector 5 can be switched off since the desorption process has been completed and presently the analyzing process can take place.
  • the cooling of the cold trap 46 can be switched off, so that the temperature in the cold trap 46 will rise rapidly to the temperature prevailing in the oven chamber O of the gas chromatograph 1.
  • the heat capacity of the cold trap is to be held low, for instance by designing the cold trap 46 as a capillary which is surrounded by a needle, through which needle liquid nitrogen can be passed.
  • the substances condensed therein will start to evaporate and be entrained by the carrier gas which is supplied to the cold trap 46 via the second carrier gas supply duct 44 and the first T-junction 49 via the first connecting duct 47.
  • the carrier gas flows via the second connecting duct 48 to the second T-junction 50 to which an inlet of the gas chromatography column 42 is connected. At least a part of the carrier gas therefore flows through the gas chromatography column 42, where a separation of the substances occurs, so that they end up successively in the detector 6, on the basis of which it can be determined what substances were present in the absorption material of the sampling tube 20.
  • stepwise raising the temperature in the oven chamber O first the light fractions can be liberated from the cold trap 46 and then the heavier fractions.
  • a sampling tube 20 has been discussed in which the inflow opening 26 and the outflow opening 25 are situated at a first end 20a of the sampling tube 20.
  • This has as an advantage that, when placing the sampling tube 20, in a very simple manner both the inflow opening 26 and the outflow opening 25 can be set in fluid communication with a carrier gas supply duct 41 and the gas chromatography column 42, respectively.
  • the sampling tube 120 is provided with an inflow opening 126 on a second end 120b and an outflow opening 125 on a first end 120a of the sampling tube 120.
  • the assembly is provided with a movable first carrier gas supply duct 141 of which an outflow opening 141a is adapted to be connectable to the inflow opening 126 of the sampling tube 120.
  • a discharge 35 is provided which, in the condition of the sampling tube 20 when placed in the chamber K, connects to the outflow opening 125 of the sampling tube 120.
  • the movable carrier gas supply duct 141 is included in a swiveling arm 53.
  • the swiveling arm 53 is provided with a carrying cam 154 which, as the sampling tube 120 is fitted, is engaged by the lower edge of the cover 140 of the sampling tube 120. With this engagement, the swiveling arm 53 gradually swivels along with the movement of the sampling tube 120, while simultaneously the outflow opening 141a of the first carrier gas supply duct 141 is pushed into the inflow opening 126 of the sampling tube 120.
  • Fig. 11 shows a position of the sampling tube 20 and the swiveling arm 53 at the beginning of the engagement
  • Fig. 12 shows the swiveling arm 53 and the sampling tube 120 in a condition in which the sampling tube 120 is disposed in the chamber K of the adapter 19.
  • the outflow opening 141a of the first carrier gas supply duct 141 has been set to connect to the inflow opening 126 of the sampling tube 120.
  • the discharge 35 has been set into fluid communication with the outflow opening 125 of the sampling tube 120.

Landscapes

  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Sampling And Sample Adjustment (AREA)

Claims (23)

  1. Adaptateur pour la désorption d'un tube d'échantillonnage (20) comportant une ouverture de débit entrant (26) et une ouverture de débit sortant (25) dans un chromatographe en phase gazeuse (1) connu en soi comportant un injecteur (5), l'adaptateur (19) étant caractérisé en ce qu'il peut être placé dans l'injecteur (5) et en ce qu'il est pourvu d'une chambre (K) qui est délimitée par un boîtier conducteur de la chaleur (29), l'adaptateur (19) étant adapté pour recevoir un tube d'échantillonnage (20) dans sa chambre (K), moyennant quoi, en utilisation, quand un tube d'échantillonnage (20) est mis en place dans l'adaptateur (19) et que l'adaptateur (19) est monté dans l'injecteur (5), l'ouverture de débit entrant (26) du tube d'échantillonnage (20) est en communication fluide avec une première conduite d'alimentation en gaz porteur (41), tandis que l'ouverture de débit sortant (25) du tube d'échantillonnage (20) est en communication fluide via l'injecteur (5) avec une colonne de chromatographie en phase gazeuse (42) disposée dans le chromatographe en phase gazeuse (1);
  2. Adaptateur selon la revendication 1, caractérisé en ce que l'adaptateur (19) est pourvu d'un tube conducteur de la chaleur (30) qui est connecté au boîtier conducteur de la chaleur (29), de telle manière que le tube (30) et le boîtier (29) sont en échange de chaleur l'un avec l'autre, tandis que le tube (30) de l'adaptateur (19), dans l'état monté de l'adaptateur (19), pénètre à l'intérieur de la chambre d'injecteur.
  3. Adaptateur selon la revendication 2, caractérisé en ce que le boîtier (29) et le tube (30) sont construits sous la forme d'une seule pièce.
  4. Adaptateur selon la revendication 2 ou 3, caractérisé en ce que dans la paroi du tube (30), un trou (28) est prévu qui, dans un état monté de l'adaptateur (19) dans l'injecteur (5), est en communication fluide avec un canal de séparation (22) de l'injecteur (5), lequel canal de séparation peut être connecté à la première conduite d'alimentation en gaz porteur (41).
  5. Ensemble pour la désorption d'un tube d'échantillonnage (20) comprenant un chromatographe en phase gazeuse (1) et un adaptateur (19) selon l'une quelconque des revendications 1 à 4, le chromatographe en phase gazeuse (1) étant connu en soi et étant pourvu d'un injecteur (5).
  6. Ensemble selon la revendication 5, caractérisé en ce que l'injecteur (5) comprend un canal de séparation (22), la première conduite d'alimentation en gaz porteur (41) étant connectée au canal de séparation (22).
  7. Ensemble selon l'une quelconque des revendications 5 et 6, caractérisé par un ensemble de soupape (43), une deuxième conduite d'alimentation en gaz porteur (44), une conduite d'alimentation principale en gaz porteur (45), dans lequel au moins une entrée de l'ensemble de soupape (43a) est connectée à la conduite d'alimentation principale en gaz porteur (45), dans lequel une première sortie (36) de l'ensemble de soupape (43) est connectée à la première conduite d'alimentation en gaz porteur (41), dans lequel une deuxième sortie (43c) de l'ensemble de soupape (43) est connectée à la deuxième conduite d'alimentation en gaz porteur (44), dans lequel l'ensemble de soupape (43) met la conduite d'alimentation principale en gaz porteur (45) en communication fluide soit avec la première conduite d'alimentation en gaz porteur (41) soit avec la deuxième conduite d'alimentation en gaz porteur (44), dans lequel l'ensemble comprend en outre un piège froid (46), qui est disposé dans la chambre de four (O) du chromatographe en phase gazeuse (1), ainsi qu'une première conduite de connexion (47) qui met la sortie de l'injecteur (7) en communication fluide avec une entrée (46a) du piège froid (46), dans lequel une deuxième conduite de connexion (48) met une sortie (46b) du piège froid (46) en communication fluide avec la colonne de chromatographie en phase gazeuse (42), dans lequel une extrémité aval de la colonne de chromatographie en phase gazeuse (42) est en communication avec un détecteur (6), dans lequel en amont du piège froid (46) et en aval de la sortie de l'injecteur, une première jonction en T (49) est placée sur la première conduite de connexion (47), à laquelle est connectée une sortie de la deuxième conduite d'alimentation en gaz porteur (44), dans lequel une deuxième jonction en T (50) est placée sur la deuxième conduite de connexion (48), à laquelle est connectée une conduite d'évacuation (51).
  8. Ensemble selon l'une quelconque des revendications 5 à 7, caractérisé en ce que les tubes d'échantillonnage (20) utilisés sont pourvus d'une ouverture de débit entrant (26) et d'une ouverture de débit sortant (25) qui sont situées sur la même extrémité (20a) du tube d'échantillonnage (20), tandis que dans une paroi du boîtier (29) de la chambre (K) de l'adaptateur (19) sont prévus à la fois une alimentation (52) et une évacuation (35) qui, dans un état où le tube d'échantillonnage (20) est placé dans la chambre (K), se connectent respectivement à l'ouverture de débit entrant (26) et à l'ouverture de débit sortant (25) du tube d'échantillonnage (20).
  9. Ensemble selon l'une quelconque des revendications 5 à 7, caractérisé en ce que les tubes d'échantillonnage (120) utilisés sont pourvus d'une ouverture de débit entrant (126) sur une deuxième extrémité (120b) et d'une ouverture de débit sortant (125) sur une première extrémité (120a) du tube d'échantillonnage (120), l'ensemble comprenant une première conduite d'alimentation en gaz porteur mobile (141) dans laquelle une ouverture de débit sortant (141a) est adaptée pour pouvoir être connectée à l'ouverture de débit entrant du tube d'échantillonnage (120), tandis que dans une paroi du boîtier (29) de la chambre (K) de l'adaptateur (19), est prévue une évacuation (35) qui, dans un état où un tube d'échantillonnage (120) est placé dans la chambre, se connecte à l'ouverture de débit sortant (125) du tube d'échantillonnage (120).
  10. Ensemble selon la revendication 9, caractérisé en ce que la première conduite d'alimentation en gaz porteur mobile (141) s'étend dans un bras pivotant (53).
  11. Ensemble selon l'une quelconque des revendications 5 à 10, caractérisé en ce que le ou chaque tube d'échantillonnage (20, 120) utilisé a la forme d'une fiole connue en soi.
  12. Ensemble selon au moins la revendication 11, caractérisé en ce que l'ensemble comprend en outre un passeur d'échantillons (8) connu en soi, lequel passeur d'échantillons (8) comprend un râtelier (10) dans lequel peuvent être placés un nombre de tubes d'échantillonnage (20, 120), tandis qu'un manipulateur (12, 13, 14) du passeur d'échantillons (8) est adapté pour saisir un tube d'échantillonnage (20, 120) sur le râtelier (10) et placer ce tube d'échantillonnage (20, 120) dans l'adaptateur (19):
  13. Ensemble selon la revendication 12, caractérisé en ce que le passeur d'échantillons (8) est monté sur une base (54) qui est connectée à un boîtier du chromatographe en phase gazeuse (1).
  14. Ensemble selon l'une quelconque des revendications 12 et 13, caractérisé en ce que le chromatographe (1) comprend deux injecteurs (7), tandis que dans chaque injecteur (5) est placé un adaptateur (19), le passeur d'échantillons (8) étant adapté pour placer un tube d'échantillonnage (20, 120) à la fois dans l'un et l'autre adaptateur (19).
  15. Ensemble selon l'une quelconque des revendications 5 à 11, comprenant en outre un tube d'échantillonnage.
  16. Ensemble selon la revendication 15, caractérisé en ce que le tube d'échantillonnage (20, 120) est rempli d'un matériau d'adsorption.
  17. Ensemble selon la revendication 15 ou 16, caractérisé en ce que le tube d'échantillonnage (20, 120) a la forme d'une fiole connue en soi.
  18. Ensemble selon l'une quelconque des revendications 15 à 17, caractérisé en ce que le tube d'échantillonnage (20, 120) est muni d'un transpondeur.
  19. Ensemble selon l'une quelconque des revendications 15 à 18, caractérisé par un tube d'échantillonnage (20) comportant une ouverture de débit entrant (26) et une ouverture de débit sortant (25) qui sont situées à une première extrémité (20a) du tube d'échantillonnage (20), tandis qu'à l'intérieur (B) du tube d'échantillonnage (20) s'étend une conduite (32) qui est connectée par une première extrémité (32a) à l'ouverture de débit entrant (26) et qui se termine par une deuxième extrémité (32b) à l'intérieur (B) du tube d'échantillonnage (20), au voisinage d'une deuxième extrémité (20b) du tube d'échantillonnage (20), située à l'opposé de la première extrémité (20a) du tube d'échantillonnage (20).
  20. Ensemble selon l'une quelconque des revendications 15 à 19, caractérisé en ce que le tube d'échantillonnage (20) est fabriqué à partir d'un matériau inerte, comme par exemple du verre, un métal, une céramique, du Teflon® (PTFE), un Vespel®.
  21. Ensemble selon la revendication 20, caractérisé en ce que le tube d'échantillonnage (20) a été fabriqué à partir de Teflon® au moyen d'un processus de moulage par injection.
  22. Jeu de pièces comprenant au moins un adaptateur (19) selon l'une quelconque des revendications 1 à 4, ainsi qu'un support (54) pour monter un passeur d'échantillons (8) connu en soi sur un chromatographe en phase gazeuse (1) connu en soi.
  23. Jeu de pièces selon la revendication 22, caractérisé par différentes conduites de gaz porteur (41, 44, 45), au moins une pièce en T (49, 50) pour former une jonction en T telle que décrite dans la revendication 7 et un ensemble de soupape (43).
EP00201813A 1999-05-21 2000-05-22 Adapteur pour désorption des tubes d'échantillonnage, arrangement d'un chromatographe en phase gazeuse et d'un adaptateur, et arrangement de pièces pour former un tel assemblage Expired - Lifetime EP1054256B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1012127A NL1012127C2 (nl) 1999-05-21 1999-05-21 Samenstel voor het desorberen van bemonsteringsbuisjes, alsmede een adaptor en bemonsteringsbuisjes kennelijk bestemd voor een dergelijk samenstel, alsmede een kit van onderdelen ter vorming van een dergelijk samenstel.
NL1012127 1999-05-21

Publications (2)

Publication Number Publication Date
EP1054256A1 EP1054256A1 (fr) 2000-11-22
EP1054256B1 true EP1054256B1 (fr) 2011-02-09

Family

ID=19769234

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00201813A Expired - Lifetime EP1054256B1 (fr) 1999-05-21 2000-05-22 Adapteur pour désorption des tubes d'échantillonnage, arrangement d'un chromatographe en phase gazeuse et d'un adaptateur, et arrangement de pièces pour former un tel assemblage

Country Status (5)

Country Link
US (2) US6442995B1 (fr)
EP (1) EP1054256B1 (fr)
AT (1) ATE498130T1 (fr)
DE (1) DE60045604D1 (fr)
NL (1) NL1012127C2 (fr)

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6598461B2 (en) * 2001-10-29 2003-07-29 Hewlett-Packard Development Company, L.P. Apparatus for, and method of using, gas chromatography inlet system for direct analysis of substances fired from an inkjet pen
US7316730B2 (en) * 2002-03-15 2008-01-08 Restek Corporation Inlet double-seal assembly
CN1806165B (zh) * 2003-04-14 2011-04-20 珀金埃尔默健康科学股份有限公司 用于抽取头部空间中蒸气的系统和方法
US7178414B1 (en) * 2004-02-27 2007-02-20 Kokosa John M Automation of liquid phase microextraction
DE102004016670B4 (de) * 2004-04-05 2006-10-26 Gerstel Systemtechnik Gmbh & Co.Kg Verfahren zur Probenaufgabe für ein Probenanalysegerät und Linerhandhabungssystem
WO2005124366A1 (fr) * 2004-06-14 2005-12-29 Parker-Hannifin Corporation Systeme et procede de manipulation robotique a outils detachables fonctionnant separement
EP1761767A1 (fr) * 2004-06-29 2007-03-14 Perkinelmer Las, Inc. Interface entre un desorbeur thermique et une colonne de chromatographie
WO2006083695A2 (fr) 2005-01-28 2006-08-10 Parker-Hannifin Corporation Sonde d'echantillonnage, dispositif de prehension et interface de systemes de gestion d'echantillons de laboratoire
US7384457B2 (en) * 2005-10-21 2008-06-10 Agilent Technologies, Inc. Seal for gas chromatography
US20080314412A1 (en) * 2005-12-05 2008-12-25 Grippo Paul M Self-Cleaning Injection Port for Analytical Applications
US8192698B2 (en) * 2006-01-27 2012-06-05 Parker-Hannifin Corporation Sampling probe, gripper and interface for laboratory sample management systems
WO2011106747A1 (fr) * 2010-02-26 2011-09-01 Perkin Elmer Health Sciences, Inc. Ensemble à jet pour une utilisation dans des détecteurs et autres dispositifs
AU2011220544B2 (en) * 2010-02-26 2015-11-12 Perkinelmer U.S. Llc Fluid chromatography injectors and injector inserts
US20110290731A1 (en) * 2010-06-01 2011-12-01 Ozbal Can C Cartridge changers and methods for utilizing the same
DE102013005710B3 (de) * 2013-03-30 2014-06-26 Forschungszentrum Jülich GmbH Thermodesorptionsadapter für die Desorption von Feststoffen zum Aufsatz auf einen Gaschromatographen
US10274464B2 (en) * 2016-02-24 2019-04-30 Phillips 66 Company System for gas chromatography temperature modulation
US10279304B2 (en) * 2016-02-24 2019-05-07 Phillips 66 Company Gas chromatography temperature modulation
US10502664B2 (en) 2016-03-08 2019-12-10 Entech Instruments Inc. Vacuum-assisted sample extraction device and method
US10849600B2 (en) 2016-03-08 2020-12-01 Entech Instruments Inc. Breath condensate and saliva analysis using oral rinse
EP3742969A1 (fr) 2018-03-06 2020-12-02 Entech Instruments Inc. Dispositif et procédé d'échantillonnage couplé à ventilateur
CN113167732A (zh) * 2018-12-12 2021-07-23 株式会社岛津制作所 硫化学发光检测器
US11906489B2 (en) 2020-03-02 2024-02-20 Entech Instruments Inc. Autosampler
DE102020111414A1 (de) * 2020-04-27 2021-10-28 Agilent Technologies, Inc. - A Delaware Corporation - Probeninjektor mit leitungsspitze, die in nadelöffnung eindringt
CN116429961B (zh) * 2023-06-13 2023-11-07 国网浙江省电力有限公司宁波供电公司 一种油色谱分析仪器及其检测方法

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3985016A (en) * 1969-12-10 1976-10-12 Shimadzu Seisakusho Ltd. Chromatograph
US4035168A (en) * 1974-07-24 1977-07-12 The Regents Of The University Of California Nonreactive inlet splitter for gas chromatography and method
US3996008A (en) * 1975-09-17 1976-12-07 Thermo Electron Corporation Specific compound detection system with gas chromatograph
US4004881A (en) * 1975-12-18 1977-01-25 General Electric Company Apparatus for generating carrier gas-test specimen vapor mixtures for delivery into a gas chromatograph
CH655798A5 (de) * 1981-06-11 1986-05-15 Sandoz Ag Probenwechsler fuer gaschromatographische analysenapparate.
US4422860A (en) * 1982-01-26 1983-12-27 Varian Associates, Inc. On-column capillary gas chromatographic injector
US4711764A (en) * 1982-10-08 1987-12-08 Analytichem International, Inc. Automatic sample injector and disposable sample cassette
US4474588A (en) * 1983-04-11 1984-10-02 Varian Associates, Inc. Unheated septumless on-column injection system for capillary gas chromatography
DE3475569D1 (en) * 1983-09-09 1989-01-12 Erba Strumentazione Multi-purpose on column injector
FR2599152B1 (fr) * 1986-05-22 1989-07-28 Flopetrol Procede et appareil d'analyse chromatographique, en particulier pour liquides petroliers
US4713963A (en) * 1986-06-26 1987-12-22 Daryl Sharp Method and device for vacuum chromatography
US5065614A (en) * 1990-07-31 1991-11-19 Rutgers University Short path thermal desorption apparatus for use in gas chromatography techniques
US5281397A (en) * 1991-03-14 1994-01-25 General Electric Company Adjustable open-split interface for a gas chromatograph and a mass spectrometer
US5191211A (en) * 1992-03-23 1993-03-02 Bridgestone/Firestone, Inc. Thermal desorption method for separating volatile additives from vulcanizable rubber
US5472670A (en) * 1993-03-05 1995-12-05 Ohio University Gas chromatography sample injector and apparatus using same
US5394733A (en) * 1994-06-24 1995-03-07 Mobil Oil Corporation Quantitative pyrolysis-gas chromatography using diamondoid compounds
US5711786A (en) * 1995-10-23 1998-01-27 The Perkin-Elmer Corporation Gas chromatographic system with controlled sample transfer
US5686656A (en) * 1996-02-27 1997-11-11 Aviv Amirav Method and device for the introduction of a sample into a gas chromatograph
US6131440A (en) * 1996-10-15 2000-10-17 Universite De Montreal Selective removal of volatile substances injected into a chromatographic packing filled column
DE19653406C1 (de) * 1996-12-20 1998-01-29 Gerstel Gmbh Verfahren zum Aufgeben von gaschromatographisch zu untersuchenden Proben und Probenaufnahmerohr
JP3669402B2 (ja) * 1997-06-23 2005-07-06 社団法人大阪府薬剤師会 ガスクロマトグラフの試料導入方法及び試料導入装置
JPH1172426A (ja) * 1997-08-29 1999-03-16 Kett Electric Lab 試料を加熱により気化させる加熱装置

Also Published As

Publication number Publication date
ATE498130T1 (de) 2011-02-15
DE60045604D1 (de) 2011-03-24
US6442995B1 (en) 2002-09-03
US6662626B2 (en) 2003-12-16
NL1012127C2 (nl) 2000-11-23
US20020157453A1 (en) 2002-10-31
EP1054256A1 (fr) 2000-11-22

Similar Documents

Publication Publication Date Title
EP1054256B1 (fr) Adapteur pour désorption des tubes d'échantillonnage, arrangement d'un chromatographe en phase gazeuse et d'un adaptateur, et arrangement de pièces pour former un tel assemblage
US7284410B2 (en) Chromatographic interface for thermal desorption systems
EP0543471B1 (fr) Appareil et procédé d'extraction avec un fluide supercritique
JP6616090B2 (ja) 固相マイクロ抽出用装置
US4422860A (en) On-column capillary gas chromatographic injector
US5932482A (en) Headspace vial apparatus and method
US5198197A (en) Apparatus and method for supercritical fluid extraction
US7712385B2 (en) Method for the preparation of samples for an analyzer and sampling station therefor
US20180202902A1 (en) Method for sampling and extracting pollutants in a fluid, sampling cartridge, sampling and extracting devices using said method
US9927333B2 (en) Method for preparing a sample for chromatographic separation processes and systems for carrying out a sample preparation
GB2550548A (en) A sampling apparatus
US10598637B2 (en) Automated thermal desorption systems configured to determine sample tube orientation and/or cap presence, and related methods
CA1055723A (fr) Systeme d'injection chromatographique
JP2006119136A (ja) 固相抽出装置とその方法
JP4653286B2 (ja) サンプリングバイアルを脱着するための組立体、前記組立体用に明白に意図されたアダプタとサンプリングバイアル、および、前記組立体を形成するための部品キット
US20130078165A1 (en) System for carrying out a sample preparaton
Davis et al. Liquid sample inlet system for gas chromatographs
EP0915334A1 (fr) Procede et appareil pour concentrer une solution
CN218331388U (zh) 一种处理环境空气样品和液体样品的前处理一体机
WO1992015853A1 (fr) Appareil chauffe de transfert d'echantillons
JPH03113364A (ja) ヘッドスペースガスサンプラ

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17P Request for examination filed

Effective date: 20010522

AKX Designation fees paid

Free format text: AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

17Q First examination report despatched

Effective date: 20080118

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RTI1 Title (correction)

Free format text: ADAPTOR FOR DESORBING SAMPLING TUBES, ASSEMBLY COMPRISING A GAS CHROMATOGRAPH AND THE ADAPTOR, AND A KIT OF PARTS FOR FORMING SUCH AN ASSEMBLY

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 60045604

Country of ref document: DE

Date of ref document: 20110324

Kind code of ref document: P

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 60045604

Country of ref document: DE

Effective date: 20110324

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110609

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110209

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110520

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110510

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110209

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110209

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110209

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110209

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110209

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110531

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

26N No opposition filed

Effective date: 20111110

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110531

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110531

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20120131

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 60045604

Country of ref document: DE

Effective date: 20111110

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110531

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110522

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110209

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20120523

Year of fee payment: 13

Ref country code: NL

Payment date: 20120516

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20120522

Year of fee payment: 13

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110522

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20131201

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20130522

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131203

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131201

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60045604

Country of ref document: DE

Effective date: 20131203

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130522